硅酸盐学报

固态电池富锂锰基层状氧化物正极材料研究进展

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孔伟进 ¹ , 沈亮 ¹ , 赵辰孜 ¹ , 乐翼成 ² , 顾一凡 ³ , 胡江奎 ⁴^,⁵ , 张强 ¹^,⁶

硅酸盐学报 | 全固态电池发展专刊—综合评述 2025,53(6): 1764-1776

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硅酸盐学报 |全固态电池发展专刊—综合评述 2025 , 53 (6) : 1764 -1776

固态电池富锂锰基层状氧化物正极材料研究进展

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孔伟进¹, 沈亮¹, 赵辰孜¹, 乐翼成², 顾一凡³, 胡江奎⁴^,⁵, 张强¹^,⁶

作者信息

^1．清华大学化学工程系，复合固态电池北京市重点实验室，北京 100084

^2．清华大学探微书院，北京 100084

^3．清华大学致理书院，北京 100084

^4．北京理工大学前沿交叉科学研究院，北京 100081

^5．智能固态电池创新中心，四川宜宾 644002

^6．清华大学碳中和研究院，北京 100084

通讯作者:

张强（1984—），男，博士，教授。

作者简介:

孔伟进（1992—），男，博士，助理研究员。

Li-Rich Mn-Based Layered Oxide Cathodes for Solid-State Rechargeable Batteries

Weijin KONG¹, Liang SHEN¹, Chenzi ZHAO¹, Yicheng LE², Yifan GU³, Jiangkui HU⁴^,⁵, Qiang ZHANG¹^,⁶

Affiliations

^1.Department of Chemical Engineering, Beijing Key Laboratory of Complex Solid State Batteries, Tsinghua University, Beijing 100084, China

^2.Tanwei College, Tsinghua University, Beijing 100084, China

^3.Zhili College, Tsinghua University, Beijing 100084, China

^4.Advanced Research Institute of Multidisciplinary Science, Beijing Institute of Technology, Beijing 100081, China

^5.Innovation Center for Smart Solid State Batteries, Yibin 644002, China

^6.Institute for Carbon Neutrality, Tsinghua University, Beijing 100084, China

Corresponding Author:

ZHANG Qiang (1984-), male, Ph.D., Professor. E-mail: zhang-qiang@mails.tsinghua.edu.cn

KONG Weijin (1992-), male, Ph.D., Assistant Research Fellow. E-mail: kwj-2022@mail.tsinghua.edu.cn

出版时间: 2025-06-20 doi: 10.14062/j.issn.0454-5648.20250145

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摘要

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固态电池是具有高能量密度和高安全性的下一代二次电池。当匹配固态电解质与金属锂负极构筑全电池时，正极材料的种类显著影响了其能量密度。富锂锰基正极材料具有较高的放电比容量，是实现更高能量密度固态电池的关键材料。当富锂锰基正极与金属锂负极匹配，有望进一步构筑能量密度大于600 W·h·kg^-1的固态电池。因此，对富锂锰基正极材料开展体相/表界面结构设计、构筑稳定快速的离子/电子通路、促进稳定阴离子氧化还原反应是实现其在固态电池中应用的重要策略。这些策略的重点在于改善多相界面的不兼容、抑制析氧和增强固|固界面高电压稳定性等问题。本文综述了固态电池富锂锰基正极材料的设计开发策略和提升正极与固态电解质固|固界面高电压稳定性问题的最新研究进展，并展望了未来富锂锰基正极材料在固态电池应用中的研究重点和重要应用场景。

关键词

固态电池 / 富锂锰基正极材料 / 能量密度 / 阴离子氧化还原反应 / 高电压界面

Abstract

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Solid-state batteries (SSBs) are a promising next-generation secondary battery due to their potential for high energy density and enhanced safety, offering solutions to the problems inherent in conventional lithium-ion batteries (LIBs) with organic liquid electrolytes (i.e., flammability, corrosion susceptibility, and high-voltage instability). In the construction of SSBs, the selection of the cathode materials is critical to achieving a high energy density, particularly when coupled with lithium metal anodes. However, conventional cathodes often affect the energy density of SSBs due to their constrained specific capacities. It is thus crucial for achieving substantial improvements in the energy density of SSBs to develop high specific capacity cathodes. The Li-rich Mn-based layered oxide (LRMO) is a promising cathode material for SSBs for energy densities of above 600 W·h·kg^-1 due to their high discharge specific capacities. Furthermore, LRMO cathodes offer some additional advantages, i.e., reduction of Co and Ni content, leverage of the abundance of Mn to achieve lower materials costs and improved safety. Their application in SSBs also mitigates the dissolution of TM-ions into the electrolyte, thereby enhancing the structural stability and capacity retention during long-term cycling progress. In addition, the resource-efficient composition of LRMO cathodes also align with environmentally friendly and sustainable development goals.

This review represents that the LRMO cathode materials are characterized by a composite crystal structure comprising two key components, i.e., Li₂MnO₃ phase and LiMO₂(M=Mn, Ni, Co) phase. Li₂MnO₃ phase can be considered as a superlattice-structured variant of LiMO₂, formulated as Li[Li_xMn₁₋_x]O₂. This superlattice-structured introduces unique unhybridized O 2p states, arising from Li—O—Li configurations. These unique oxygen states enable the participation of oxygen in charge compensation processes. Consequently, the high capacity in LRMO cathodes is attributed to the synergistic contributions of both TM cations and oxygen redox reactions.

LRMO cathodes, while exhibiting a distinctive biphasic structure, encounter significantly some challenges in SSBs. Specifically, the application of LRMO cathodes in SSBs is hindered by two primary issues. Firstly, the inherent incompatibility between Li₂MnO₃ phase and SEs interfaces results in sluggish reaction kinetics, severely restricting the activation of oxygen redox activity and consequently reducing the associated capacity contribution. Secondly, a chemical potential mismatch between SEs and LRMO cathodes drives spontaneous reactions at the composite cathode interfaces. These reactions lead to the formation of mixed ionic/electronic conductive CEI. Furthermore, irreversible oxygen escape further oxidizes the SEs interface, generating the passivation layers. These passivation layers increase interfacial impedance and imped ion transport, ultimately hindering practical advancements in SSBs technology.

LRMO cathodes hold a significant promise for SSBs, as evidenced by research progress across various SEs, including sulfides, halides, polymers, and oxides. To fully realize this potential, some strategies addressing the inherent incompatibility between LRMO cathodes and SEs are crucial. These strategies encompass bulk/interfacial structure design, nanostructured particle engineering, and the construction of stable Li⁺/e^- transport pathways. These approaches can suppress oxygen escape, enhance the high-voltage stability of solid-solid interfaces, and ultimately stabilize oxygen redox while optimizing interfacial dynamics. Consequently, the implementation of these strategies leads to a significant enhancement in the electrochemical performance of LRMO-based SSBs.

Summary and prospects

LRMO cathodes have attracted considerable attention for SSBs due to their high discharge specific capacity and energy density. Advancements in SSBs utilizing sulfide, halide, polymer, and oxide SEs demonstrate a potential of LRMO cathodes to overcome limitations currently hindering their industrial applications in liquid electrolyte systems. These limitations include gas evolution, TM dissolution, and voltage decay. However, the practical application of LRMO cathodes in SSBs faces some challenges stemming from their inherent properties, such as poor electronic conductivity attributed to their biphasic structure, sluggish interfacial charge transfer kinetics, oxygen escape, high-voltage interfacial instability, and electrochemical-mechanical degradation. Consequently, a comprehensive understanding of failure mechanisms and the development of advanced modification strategies for LRMO cathodes in SSBs are urgently needed. This necessitates several key research directions. Firstly, optimizing large-scale synthesis techniques for single-crystal LRMO cathodes is crucial, coupled with systematic investigation into their degradation mechanisms within SSBs. Such studies should elucidate the complex interplay of mechanical, electrical, and chemical coupling within SSBs. Secondly, the development of zero-strain LRMO cathodes, designed to maintain structural integrity with minimal volume changes during cycling, can effectively mitigate mechanical stress, suppress crack formation (both intergranular and intragranular), and significantly improve long-term cycling stability. Furthermore, machine learning-driven multiscale modeling offers an effective tool for the rational design of bulk/interfacial structures, facilitating superior compatibility and high-voltage stability at the solid-solid interfaces. Finally, the exploration of high-voltage-tolerant SEs specifically tailored for LRMO cathodes, alongside innovations in scalable fabrication processes for ultrathin electrolyte membranes and electrode films, is essential. The synergistic convergence of materials innovation, interfacial engineering and scalable manufacturing offers a transformative potential for realizing the full capabilities of LRMO cathodes. This convergence is crucial for advancing SSBs toward unprecedented levels of energy density, reliability and sustainability. Specifically, these combined efforts will facilitate the production of large-format batteries at the A·h-level, ultimately enabling the large-scale commercialization of SSBs incorporating LRMO cathodes.

Key words

solid-state batteries / lithium-rich manganese-based cathode materials / energy density / oxygen redox / high-voltage interface

引用本文

孔伟进, 沈亮, 赵辰孜, 乐翼成, 顾一凡, 胡江奎, 张强. 固态电池富锂锰基层状氧化物正极材料研究进展. 硅酸盐学报, 2025 , 53 (6) : 1764 -1776 . DOI: 10.14062/j.issn.0454-5648.20250145

Weijin KONG, Liang SHEN, Chenzi ZHAO, Yicheng LE, Yifan GU, Jiangkui HU, Qiang ZHANG. Li-Rich Mn-Based Layered Oxide Cathodes for Solid-State Rechargeable Batteries[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (6) : 1764 -1776 . DOI: 10.14062/j.issn.0454-5648.20250145

基金

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国家重点研发计划(2021YFB2500300)
国家自然科学基金(22409113; 22393904; 22393900; 22393903)
中国博士后科学基金面上项目(2023M731864)
华能集团科技项目(HNKJ23-H71)
清华大学自主科研经费
新基石科学基金会
清华大学“水木学者”资助计划

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2025年第53卷第6期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250145

接收时间：2025-03-06
首发时间：2026-10-22
出版时间：2025-06-20

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出版历史

收稿日期：2025-03-06
修回日期：2025-04-10

基金

国家重点研发计划(2021YFB2500300)

国家自然科学基金(22409113; 22393904; 22393900; 22393903)

中国博士后科学基金面上项目(2023M731864)

华能集团科技项目(HNKJ23-H71)

清华大学自主科研经费

新基石科学基金会

清华大学“水木学者”资助计划

作者信息

^1．清华大学化学工程系，复合固态电池北京市重点实验室，北京 100084

^2．清华大学探微书院，北京 100084

^3．清华大学致理书院，北京 100084

^4．北京理工大学前沿交叉科学研究院，北京 100081

^5．智能固态电池创新中心，四川宜宾 644002

^6．清华大学碳中和研究院，北京 100084

通讯作者:

张强（1984—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250145

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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